JP2002234800A - Method of producing silicon carbide single crystal and silicon carbide single crystal - Google Patents
Method of producing silicon carbide single crystal and silicon carbide single crystalInfo
- Publication number
- JP2002234800A JP2002234800A JP2001030477A JP2001030477A JP2002234800A JP 2002234800 A JP2002234800 A JP 2002234800A JP 2001030477 A JP2001030477 A JP 2001030477A JP 2001030477 A JP2001030477 A JP 2001030477A JP 2002234800 A JP2002234800 A JP 2002234800A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- single crystal
- arsenic
- carbide single
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば、半導体装
置や発光ダイオード等の構成材料に利用することができ
る炭化珪素単結晶とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon carbide single crystal which can be used as a constituent material of, for example, a semiconductor device or a light emitting diode, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】炭化珪素（ＳｉＣ）は、広いバンドギャ
ップを有すること、熱的・機械的に安定した特性を有す
ることから、半導体基板材料として、各種用途への応用
が期待されている。このようなＳｉＣの単結晶を成長さ
せる方法に、昇華再結晶法があり、ＳｉＣ単結晶よりな
る種結晶上にＳｉＣ原料粉末の加熱昇華ガスを供給し
て、ＳｉＣ単結晶を成長させている。昇華再結晶法で
は、ＳｉＣ単結晶の成長雰囲気や成長条件を制御するこ
とにより、結晶多形や電気的・物理的性質が制御可能で
あることが知られており、所望の特性を備える高品質の
ＳｉＣ単結晶を得るために、種々の改良方法が提案され
ている。2. Description of the Related Art Since silicon carbide (SiC) has a wide band gap and stable characteristics thermally and mechanically, it is expected to be applied to various uses as a semiconductor substrate material. As a method of growing such a SiC single crystal, there is a sublimation recrystallization method, in which a heated sublimation gas of a SiC raw material powder is supplied onto a seed crystal made of a SiC single crystal to grow the SiC single crystal. In the sublimation recrystallization method, it is known that by controlling the growth atmosphere and growth conditions of the SiC single crystal, the crystal polymorphism and the electrical and physical properties can be controlled. In order to obtain a SiC single crystal, various improved methods have been proposed.
【０００３】例えば、特開平６−１６９８号公報には、
ＳｉＣ原料粉末に遷移金属の珪素化合物を添加すること
により、Ｓｉ蒸気圧を一定に保ち、欠陥等を防止して結
晶性、均質性を向上させる方法が、特開平５−２２１７
９６号公報には、ＳｉＣ原料粉末にアルミニウムを添加
し、窒素を含む不活性ガス雰囲気下で、雰囲気圧力の変
化を制御しながら成長させることにより、多形の制御さ
れたＳｉＣ単結晶を得る方法が記載されている。また、
特表２０００−５０３９６８号公報には、無色のＳｉＣ
単結晶を得るために、ｎ型ドーパントとｐ型ドーパント
を添加する方法が記載されている。For example, JP-A-6-1698 discloses that
JP-A-5-2217 discloses a method of adding a silicon compound of a transition metal to a SiC raw material powder to maintain a constant Si vapor pressure, prevent defects, etc., and improve crystallinity and homogeneity.
No. 96 discloses a method for obtaining a polymorphically controlled SiC single crystal by adding aluminum to a SiC raw material powder and growing the same in an inert gas atmosphere containing nitrogen while controlling the change in atmospheric pressure. Is described. Also,
JP-T-2000-503968 discloses a colorless SiC.
A method of adding an n-type dopant and a p-type dopant to obtain a single crystal is described.
【０００４】また、得られるＳｉＣ単結晶の抵抗率は、
雰囲気ガス中に不純物を添加することによって制御可能
であることが知られている。図７は、この方法によるＳ
ｉＣ単結晶の成長に用いられる装置構成を示すもので、
図中、結晶製造装置１０は、ＳｉＣ原料粉末５を収容し
た黒鉛容器１ａを有し、黒鉛容器１ａ内に設けた黒鉛台
座２には、種結晶となるＳｉＣ単結晶基板３が接合固定
されている。ＳｉＣ原料粉末５は、黒鉛容器１ａをＳｉ
Ｃの昇華温度以上に加熱することによって、原料ガス５
ａとなって上昇し、ＳｉＣ単結晶基板３上で再結晶す
る。また、黒鉛容器１ａ上部壁には、不純物として例え
ば窒素を含むガス８ｂが導入される導入路１２が形成さ
れており、該導入路１２を経て導入される窒素はＳｉＣ
のＣサイトに置換されてｎ型ドーパントとして作用し、
その抵抗率を低下させる。The resistivity of the obtained SiC single crystal is
It is known that control is possible by adding impurities to the atmospheric gas. FIG. 7 shows S
FIG. 4 shows an apparatus configuration used for growing an iC single crystal;
In the figure, a crystal production apparatus 10 has a graphite container 1a containing a SiC raw material powder 5, and a SiC single crystal substrate 3 serving as a seed crystal is bonded and fixed to a graphite pedestal 2 provided in the graphite container 1a. I have. The SiC raw material powder 5 is obtained by charging the graphite container 1a with Si.
By heating above the sublimation temperature of C, the raw material gas 5
The temperature rises as a, and recrystallizes on the SiC single crystal substrate 3. In addition, an introduction path 12 through which a gas 8b containing, for example, nitrogen as an impurity is introduced is formed in the upper wall of the graphite container 1a, and nitrogen introduced through the introduction path 12 is SiC
To act as an n-type dopant,
Decrease its resistivity.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記図
７に示した方法に基づき、６Ｈ型のＳｉＣ単結晶を種結
晶として成長試験を行ったところ、得られるＳｉＣ単結
晶４ｂは結晶歪が大きいものであること、また、ＳｉＣ
単結晶４ｂの成長過程において、部分的に１５Ｒ型Ｓｉ
Ｃが成長する場合があることが判明した。これはＣサイ
トに置換される窒素の原子半径が炭素より小さいため、
面間隔が小さくなって結晶に歪を生じさせるものと考え
られる。そして、歪が大きくなると、結晶としての安定
性を保とうとして、６Ｈ型よりも面間隔の小さい１５Ｒ
型を成長させる、と推察されている。However, when a growth test was performed using a 6H-type SiC single crystal as a seed crystal based on the method shown in FIG. 7, the obtained SiC single crystal 4b had a large crystal strain. And SiC
In the process of growing the single crystal 4b, 15R-type Si
It has been found that C may grow. This is because the atomic radius of nitrogen substituted on the C site is smaller than carbon,
It is considered that the interplanar spacing is reduced, causing strain in the crystal. When the strain increases, 15R having a smaller interplanar spacing than the 6H type is used in order to maintain the stability as a crystal.
It is speculated that the mold will grow.
【０００６】このように、異種多形が発生すると、所望
の結晶多形を有し欠陥の少ない良質なＳｉＣ単結晶を広
い面積で得ることが困難になる。As described above, when a heterogeneous polymorph occurs, it becomes difficult to obtain a high-quality SiC single crystal having a desired crystal polymorph and having few defects over a wide area.
【０００７】そこで、本発明は、抵抗率の制御性と多形
制御性を両立させ、結晶に圧縮や拡大による歪が生じ
て、異種多形が発生するのを防止し、高品質かつ低抵抗
率なＳｉＣ単結晶を製造する方法を提供することを目的
とするものである。Accordingly, the present invention provides both a controllability of resistivity and a controllability of polymorphism, and prevents a crystal from being distorted by compression or expansion, thereby preventing heterogeneous polymorphism from occurring. It is an object of the present invention to provide a method for producing a SiC single crystal with high efficiency.
【０００８】[0008]
【課題を解決するための手段】請求項１に記載の発明
は、種結晶となる炭化珪素単結晶基板上に、炭化珪素原
料ガスを供給して炭化珪素単結晶を成長させる炭化珪素
単結晶の製造方法において、上記炭化珪素原料ガスに砒
素または砒素化合物を添加することを特徴としている。According to the first aspect of the present invention, a silicon carbide single crystal for growing a silicon carbide single crystal by supplying a silicon carbide source gas onto a silicon carbide single crystal substrate serving as a seed crystal is provided. The manufacturing method is characterized in that arsenic or an arsenic compound is added to the silicon carbide source gas.
【０００９】炭化珪素のＳｉサイトに入るｎ型ドーパン
トである砒素は、珪素と同等の原子半径を有しているた
め、置換によって結晶を圧縮または拡大させることがな
く、結晶内歪を生じにくい。その結果、異種多形の発生
を抑制し、所望の抵抗率でかつ良質の炭化珪素単結晶が
得られる。Arsenic, which is an n-type dopant entering the Si site of silicon carbide, has an atomic radius equivalent to that of silicon, so that substitution does not compress or expand the crystal, and hardly causes intra-crystal distortion. As a result, the occurrence of heterogeneous polymorphism is suppressed, and a silicon carbide single crystal having a desired resistivity and good quality can be obtained.
【００１０】請求項２のように、具体的には、容器内
に、上記炭化珪素単結晶基板と、上記原料炭化珪素ガス
の供給源となる炭化珪素原料粉末を配置し、該炭化珪素
原料粉末に砒素または砒素化合物を添加する。これによ
り、容易に上記炭化珪素原料ガスに砒素または砒素化合
物を添加することができ、均一に混合した原料ガスが上
記炭化珪素単結晶基板に達するので、結晶内に均一に取
り込まれ、局所的な歪の発生等を抑制できる。Specifically, the silicon carbide single crystal substrate and the silicon carbide raw material powder serving as a source of the raw material silicon carbide gas are arranged in a container, and the silicon carbide raw material powder is provided. Arsenic or an arsenic compound. As a result, arsenic or an arsenic compound can be easily added to the silicon carbide source gas, and the uniformly mixed source gas reaches the silicon carbide single crystal substrate. Generation of distortion can be suppressed.
【００１１】あるいは、請求項３のように、容器内に、
上記炭化珪素単結晶基板を配置し、上記容器内に砒素ま
たは砒素化合物を含有する部材を配置するか、あるい
は、上記容器の少なくとも内表面に砒素または砒素化合
物を含有させることにより、上記炭化珪素原料ガスに砒
素または砒素化合物を添加してもよい。例えば、上記容
器の構成材料中、または、上記容器の内表面に形成され
るコーティング層に、砒素または砒素化合物を添加する
ことができ、均一に混合した原料ガスが上記炭化珪素単
結晶基板に達するので、結晶内に均一に取り込まれ、局
所的な歪の発生等を抑制できる。Alternatively, as in claim 3, in the container,
By disposing the silicon carbide single crystal substrate and disposing a member containing arsenic or an arsenic compound in the container, or by including arsenic or an arsenic compound on at least the inner surface of the container, the silicon carbide raw material is obtained. Arsenic or an arsenic compound may be added to the gas. For example, arsenic or an arsenic compound can be added to the constituent material of the container or to the coating layer formed on the inner surface of the container, and the uniformly mixed source gas reaches the silicon carbide single crystal substrate. Therefore, it is uniformly taken into the crystal, and the occurrence of local distortion can be suppressed.
【００１２】さらに、請求項４のように、容器内に、上
記炭化珪素単結晶基板を配置し、上記容器内に砒素また
は砒素化合物を含有するガスを供給することにより、上
記炭化珪素原料ガスに砒素または砒素化合物を添加する
こともできる。ガス状であるため、混合が容易で、均一
に混合した原料ガスが上記炭化珪素単結晶基板に達して
結晶内に均一に取り込まれ、局所的な歪の発生等を抑制
する効果がある。Further, the silicon carbide single crystal substrate is disposed in a container, and a gas containing arsenic or an arsenic compound is supplied into the container, so that the silicon carbide raw material gas is supplied to the silicon carbide raw material gas. Arsenic or an arsenic compound can also be added. Since it is in a gaseous state, mixing is easy, and the uniformly mixed raw material gas reaches the silicon carbide single crystal substrate and is uniformly taken into the crystal, which has the effect of suppressing local distortion and the like.
【００１３】請求項５の発明では、種結晶となる炭化珪
素単結晶基板上に、炭化珪素原料ガスを供給して炭化珪
素単結晶を成長させる炭化珪素単結晶の製造方法におい
て、上記炭化珪素原料ガスに、珪素より小さな原子半径
を有するｎ型ドーパント原子またはその化合物と、珪素
より大きな原子半径を有する軽金属を除く金属原子また
はその化合物を添加することを特徴とする。According to a fifth aspect of the present invention, in the method for producing a silicon carbide single crystal in which a silicon carbide raw material gas is supplied onto a silicon carbide single crystal substrate serving as a seed crystal, the silicon carbide single crystal is grown. The gas is characterized by adding an n-type dopant atom or a compound thereof having an atomic radius smaller than silicon and a metal atom or a compound thereof excluding a light metal having an atomic radius larger than silicon.
【００１４】珪素より小さな原子半径を有するｎ型ドー
パント原子は結晶の圧縮作用を有する。そこで、ｎ型ド
ーパント原子によって抵抗率を制御する場合、珪素より
大きな原子半径を有する軽金属を除く金属原子を添加す
ると、Ｓｉ位置に置換される上記金属原子が結晶の拡大
作用を有するため、ｎ型ドーパント原子の圧縮作用を打
ち消す効果を示す。軽金属は珪素との原子半径の差が大
きく結晶欠陥の原因となり得るので好ましくない。よっ
て、結晶内歪を緩和して、異種多形の発生を抑制し、所
望の抵抗率でかつ良質の炭化珪素単結晶が得られる。An n-type dopant atom having an atomic radius smaller than that of silicon has a crystal compressing action. Therefore, in the case where the resistivity is controlled by the n-type dopant atom, if a metal atom other than a light metal having an atomic radius larger than silicon is added, the metal atom substituted at the Si position has an action of expanding the crystal. The effect of counteracting the compressive action of dopant atoms is shown. Light metals are not preferred because they have a large difference in atomic radius from silicon and can cause crystal defects. Therefore, the strain in the crystal is relaxed, the occurrence of heterogeneous polymorphism is suppressed, and a silicon carbide single crystal having a desired resistivity and good quality can be obtained.
【００１５】請求項６のように、上記金属原子の添加量
は、上記ｎ型ドーパント原子の添加量より少なく、上記
ｎ型ドーパント原子により生じる結晶内歪を緩和するた
めに必要な量以上とする。ｎ型ドーパント原子の添加に
よる効果を保持するには、上記金属原子の添加量はでき
るだけ少ない方がよく、結晶内歪の緩和効果と両立する
ように適宜選択することが好ましい。According to a sixth aspect of the present invention, the addition amount of the metal atom is smaller than the addition amount of the n-type dopant atom, and is not less than an amount necessary for relaxing the intra-crystal distortion caused by the n-type dopant atom. . In order to maintain the effect of the addition of the n-type dopant atom, the addition amount of the metal atom is preferably as small as possible, and it is preferable that the addition amount is appropriately selected so as to be compatible with the effect of alleviating the strain in the crystal.
【００１６】請求項７のように、具体的には、上記ｎ型
ドーパント原子として、窒素およびリンから選ばれる少
なくとも１つを用いることができる。ＳｉＣのＣサイト
に入る窒素、Ｓｉサイトに入るリンはともに結晶を圧縮
させるが、この圧縮量は上記金属原子の添加により緩和
できる量であり、両者の組み合わせによって結晶歪を低
減可能である。Specifically, at least one selected from nitrogen and phosphorus can be used as the n-type dopant atom. Both nitrogen entering the C site of SiC and phosphorus entering the Si site compress the crystal, and the amount of compression can be relaxed by the addition of the above-described metal atoms, and the combination of the two can reduce the crystal distortion.
【００１７】請求項８のように、上記金属原子として
は、原子半径が１．１７オングストローム以上、１．６
０オングストローム以下の原子が好適に用いられ、結晶
内歪の緩和する効果を発揮する。上記結晶の拡大作用を
有するためには、原子半径が１．１７オングストローム
以上であることが必要である。一方、原子半径が１．６
０オングストロームより大きいと結晶欠陥の原因となり
得るため、好ましくない。According to the present invention, the metal atom has an atomic radius of 1.17 angstroms or more and 1.6 or more.
Atoms of 0 Å or less are preferably used and exhibit an effect of alleviating intra-crystal distortion. In order to have the effect of expanding the crystal, the atomic radius must be 1.17 Å or more. On the other hand, the atomic radius is 1.6
If the thickness is larger than 0 Å, crystal defects may be caused, which is not preferable.
【００１８】請求項９のように、上記金属原子の具体例
としては、チタン、バナジウムおよびタンタルから選ば
れる少なくとも１つが挙げられる。ＳｉＣのＳｉサイト
に入るこれら金属原子は、Ｓｉ（１．１７オングストロ
ーム）に対して、原子半径が１．３５〜１．４７オング
ストロームと大きいため、わずかな添加量で拡大効果を
得ることができる。As a ninth aspect, a specific example of the metal atom is at least one selected from titanium, vanadium and tantalum. Since these metal atoms entering the Si site of SiC have an atomic radius of 1.35 to 1.47 angstroms which is larger than that of Si (1.17 angstroms), the effect of expansion can be obtained with a small addition amount.
【００１９】請求項１０のように、具体的には、容器内
に、上記炭化珪素単結晶基板を配置し、上記容器内に上
記ｎ型ドーパント原子またはその化合物を含有するガス
を供給する。これにより、容易に上記炭化珪素原料ガス
に上記ｎ型ドーパント原子またはその化合物を添加する
ことができ、均一に混合した原料ガスが上記炭化珪素単
結晶基板に達するので、結晶内に均一に取り込まれ、局
所的な歪の発生等を抑制できる。Specifically, the silicon carbide single crystal substrate is placed in a container, and a gas containing the n-type dopant atom or a compound thereof is supplied into the container. Thereby, the n-type dopant atom or its compound can be easily added to the silicon carbide source gas, and the uniformly mixed source gas reaches the silicon carbide single crystal substrate, so that it is uniformly taken into the crystal. And the occurrence of local distortion can be suppressed.
【００２０】または、請求項１１のように、容器内に、
上記炭化珪素単結晶基板と、上記原料炭化珪素ガスの供
給源となる炭化珪素原料粉末を配置し、該炭化珪素原料
粉末に上記金属原子またはその化合物を添加する。この
場合も、混合が容易で、均一に混合した原料ガスが上記
炭化珪素単結晶基板に達するので、結晶内に均一に取り
込まれ、局所的な歪の発生等を抑制できる。[0020] Alternatively, as in claim 11, in the container,
The silicon carbide single crystal substrate and the silicon carbide raw material powder serving as a supply source of the raw material silicon carbide gas are arranged, and the metal atom or the compound thereof is added to the silicon carbide raw material powder. Also in this case, mixing is easy, and the uniformly mixed raw material gas reaches the silicon carbide single crystal substrate, so that the raw material gas is uniformly taken into the crystal, and local distortion can be suppressed.
【００２１】または、請求項１２のように、上記炭化珪
素単結晶基板を配置し、上記容器内に、上記金属原子ま
たはその化合物を含有する部材を配置するか、あるい
は、上記容器の少なくとも内表面に上記金属原子または
その化合物を含有させる。このようにしても、上記炭化
珪素原料ガスに上記金属原子またはその化合物を添加す
ることができ、結晶内に均一に取り込まれ、局所的な歪
の発生等を抑制する同様の効果が得られる。According to a twelfth aspect of the present invention, the silicon carbide single crystal substrate is disposed, and a member containing the metal atom or its compound is disposed in the container, or at least an inner surface of the container is provided. Contains the above metal atom or its compound. Even in this case, the metal atom or the compound thereof can be added to the silicon carbide source gas, and the same effect can be obtained that the metal atom or the compound is uniformly taken into the crystal and suppresses the occurrence of local distortion.
【００２２】請求項１３のように、容器内に、上記炭化
珪素単結晶基板を配置し、上記容器内に上記金属原子ま
たはその化合物を含有するガスを供給することもでき
る。ガス状で添加することにより、上記炭化珪素原料ガ
スに上記金属原子またはその化合物を容易に添加混合で
き、結晶内に均一に取り込まれ、局所的な歪の発生等を
抑制する同様の効果が得られる。According to a thirteenth aspect, the silicon carbide single crystal substrate can be arranged in a container, and a gas containing the metal atom or its compound can be supplied into the container. By adding in a gaseous state, the above-mentioned metal atom or its compound can be easily added to and mixed with the above-mentioned silicon carbide raw material gas, uniformly taken in the crystal, and a similar effect of suppressing the occurrence of local distortion can be obtained. Can be
【００２３】請求項１４の発明は、結晶構造中に砒素を
含有することを特徴とする炭化珪素単結晶である。上記
請求項１と同様の効果により、歪の少ない結晶が得ら
れ、異種多形の発生を抑制して、所望の抵抗率でかつ良
質の炭化珪素単結晶が得られる。A fourteenth aspect of the present invention is a silicon carbide single crystal characterized in that arsenic is contained in the crystal structure. By the same effect as in the first aspect, a crystal with less distortion can be obtained, and the generation of heterogeneous polymorphs can be suppressed, and a silicon carbide single crystal having desired resistivity and good quality can be obtained.
【００２４】請求項１５のように、上記効果を得るに
は、炭化珪素単結晶中の砒素濃度を、１×１０16ｃｍ-3
以上、１×１０20ｃｍ-3以下とすることが望ましい。According to a fifteenth aspect, in order to obtain the above effect, the arsenic concentration in the silicon carbide single crystal is set to 1 × 10 16 cm −3.
As described above, it is desirable that the density be 1 × 10 20 cm −3 or less.
【００２５】請求項１６の発明は、結晶構造中に、珪素
より小さな原子半径を有するｎ型ドーパント原子と、珪
素より大きな原子半径を有する軽金属を除く金属原子を
含有することを特徴とする炭化珪素単結晶である。上記
請求項５と同様の効果により、ｎ型ドーパント原子によ
る歪を上記金属原子が打ち消すことにより、歪を緩和し
て異種多形の発生を抑制し、所望の抵抗率でかつ良質の
炭化珪素単結晶が得られる。The invention of claim 16 is characterized in that the crystal structure contains an n-type dopant atom having an atomic radius smaller than silicon and a metal atom excluding a light metal having an atomic radius larger than silicon. It is a single crystal. According to the same effect as in the fifth aspect, the metal atom cancels out the strain caused by the n-type dopant atom, thereby relaxing the strain and suppressing the generation of heterogeneous polymorphs, thereby obtaining a silicon carbide monolayer having a desired resistivity and good quality. Crystals are obtained.
【００２６】請求項１７のように、上記効果を得るに
は、上記ｎ型ドーパント原子濃度が、１×１０16ｃｍ-3
以上、１×１０20ｃｍ-3以下であることが望ましい。According to a seventeenth aspect, in order to obtain the above effect, the n-type dopant atom concentration is set to 1 × 10 16 cm −3.
As described above, it is desirable that the density be 1 × 10 20 cm −3 or less.
【００２７】また、請求項１８のように、上記金属原子
濃度は、１×１０14ｃｍ-3以上、１×１０18ｃｍ-3以下
とすることが好ましい。[0027] Further, it is preferable that the metal atom concentration is set to 1 × 10 14 cm −3 or more and 1 × 10 18 cm −3 or less.
【００２８】[0028]
【発明の実施の形態】以下、本発明のＳｉＣ単結晶の製
造方法を、図面に基づいて説明する。図１は、本発明の
第１実施形態で用いる装置の構成を示す図で、結晶製造
装置１０は、黒鉛容器１と、その上端開口を閉鎖する蓋
体を兼ねる黒鉛台座２を有している。黒鉛台座２の下面
中央には、種結晶となるＳｉＣ単結晶基板３が接合固定
してあり、黒鉛容器１の下半部内に充填されるＳｉＣ原
料粉末５と対向している。黒鉛容器１は、両端開口の筒
状体内に、ＳｉＣ原料粉末５を保持する有底の容器体を
装着した構造となっている。なお、結晶製造装置１０
は、黒鉛容器１を収容する真空容器（図略）を有し、こ
の真空容器を真空排気系およびガス供給系に接続するこ
とにより、黒鉛容器１内の雰囲気や圧力を制御できるよ
うになっている。また、黒鉛容器１は、外周に配置され
る加熱装置（図略）によって加熱できるようになってお
り、加熱装置への投入パワー等を調節することによって
黒鉛容器１内の温度を制御可能である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for producing a SiC single crystal according to the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing a configuration of an apparatus used in a first embodiment of the present invention. A crystal manufacturing apparatus 10 has a graphite container 1 and a graphite pedestal 2 serving also as a lid closing an upper end opening thereof. . At the center of the lower surface of the graphite pedestal 2, a SiC single crystal substrate 3 serving as a seed crystal is bonded and fixed, and faces the SiC raw material powder 5 filled in the lower half of the graphite container 1. The graphite container 1 has a structure in which a bottomed container that holds the SiC raw material powder 5 is mounted in a cylindrical body that is open at both ends. The crystal manufacturing apparatus 10
Has a vacuum container (not shown) for accommodating the graphite container 1, and by connecting this vacuum container to a vacuum exhaust system and a gas supply system, the atmosphere and pressure in the graphite container 1 can be controlled. I have. Further, the graphite container 1 can be heated by a heating device (not shown) arranged on the outer periphery, and the temperature in the graphite container 1 can be controlled by adjusting the input power to the heating device and the like. .
【００２９】本実施の形態では、黒鉛容器１内に収容さ
れるＳｉＣ原料粉末５中に、予め、砒素または砒素化合
物６を添加混合する。この砒素または砒素化合物６を含
有するＳｉＣ原料粉末５を加熱昇華させると、ＳｉＣ原
料ガス５ａに、砒素または砒素化合物を含むガス６ａが
混入することにより、砒素を含有するＳｉＣ単結晶４ａ
が成長する。砒素または砒素化合物６としては、例え
ば、金属砒素等が好適に用いられる。In the present embodiment, arsenic or an arsenic compound 6 is previously added to and mixed with the SiC raw material powder 5 contained in the graphite container 1. When the SiC raw material powder 5 containing the arsenic or the arsenic compound 6 is heated and sublimated, the gas 6a containing the arsenic or the arsenic compound is mixed into the SiC raw material gas 5a, so that the arsenic-containing SiC single crystal 4a
Grows. As the arsenic or the arsenic compound 6, for example, metal arsenic is preferably used.
【００３０】砒素は、ＳｉＣのＳｉサイトに置換されて
ｎ型ドーパントとして作用し、得られるＳｉＣ単結晶４
ａの抵抗値を低減させる。この時、砒素は原子半径が
１．１８オングストロームと、珪素の原子半径（１．１
７オングストローム）と同等であるため、砒素の添加に
よる結晶の圧縮ないし拡大は生じない。従って、結晶歪
の小さいＳｉＣ単結晶４ａが得られ、歪による異種多形
の発生や欠陥の発生が抑制される。Arsenic replaces the Si site of SiC and acts as an n-type dopant, and the resulting SiC single crystal 4
The resistance value of a is reduced. At this time, arsenic has an atomic radius of 1.18 angstroms and silicon has an atomic radius (1.1
7 angstrom), so that compression or expansion of the crystal due to the addition of arsenic does not occur. Therefore, a SiC single crystal 4a having a small crystal strain is obtained, and generation of heterogeneous polymorphism and generation of defects due to the distortion are suppressed.
【００３１】ＳｉＣ単結晶４ａ中の砒素濃度は、１×１
０16ｃｍ-3以上、１×１０20ｃｍ-3以下とすることが好
ましく、この範囲で、所望の低抵抗値となるように適宜
選択することができる。砒素濃度が１×１０16ｃｍ-3未
満であると、抵抗値の低減効果が得られず、１×１０20
ｃｍ-3を越えるとＳｉＣ特性への悪影響が懸念される。The arsenic concentration in the SiC single crystal 4a is 1 × 1
It is preferable that the resistivity be 0 16 cm −3 or more and 1 × 10 20 cm −3 or less, and within this range, it can be appropriately selected so as to have a desired low resistance value. When the arsenic concentration is less than 1 × 10 16 cm -3, the effect of reducing the resistance value can not be obtained, 1 × 10 20
If it exceeds cm -3 , there is a concern that the SiC characteristics will be adversely affected.
【００３２】上記結晶製造装置１０を用いたＳｉＣ単結
晶の製造方法について説明する。まず、図略の真空容器
に導入した不活性ガスを、黒鉛容器１の１〜１０ｍｍの
隙間から内部に導入し、さらに、図略の加熱装置によ
り、ＳｉＣ原料粉末５の温度を、通常、２０００〜２５
００℃に加熱する。その際、加熱装置の調節等により、
ＳｉＣ単結晶基板３の温度がＳｉＣ原料粉末５の温度よ
りも低くなるように、黒鉛容器１内に温度勾配を設け
る。次に、黒鉛容器１内の圧力を徐々に減圧していく
と、０．１〜１００Ｔｏｒｒ（１３．３Ｐａ〜１３．３
ｋＰａ）に到達したところで、昇華法成長が開始され
る。A method for producing a SiC single crystal using the above crystal producing apparatus 10 will be described. First, an inert gas introduced into a vacuum vessel (not shown) is introduced into the interior of the graphite vessel 1 through a gap of 1 to 10 mm, and the temperature of the SiC raw material powder 5 is usually raised to 2000 by a heating device (not shown). ~ 25
Heat to 00 ° C. At that time, by adjusting the heating device, etc.
A temperature gradient is provided in the graphite container 1 so that the temperature of the SiC single crystal substrate 3 is lower than the temperature of the SiC raw material powder 5. Next, when the pressure in the graphite container 1 is gradually reduced, the pressure becomes 0.1 to 100 Torr (13.3 Pa to 13.3).
kPa), the sublimation growth is started.
【００３３】具体的には、ＳｉＣ原料粉末５が昇華し
て、気相種Ｓｉ、ＳｉＣ2 、Ｓｉ2 Ｃ等を含む原料ガス
５ａとなり、上方のＳｉＣ単結晶基板３に輸送されて、
相対的に低温となるＳｉＣ単結晶基板３表面にて、再結
晶化する。同時に、ＳｉＣ原料粉末５中に予め添加され
ている、砒素または砒素化合物６が昇華または蒸発し
て、砒素または砒素化合物を含むガス６ａとなる。砒素
または砒素化合物を含むガス６ａは、原料ガス５ａと混
合された後、原料ガス５ａとともにＳｉＣ単結晶基板３
に輸送され、成長するＳｉＣ単結晶４ａにｎ型ドーパン
トとして取り込まれる。More specifically, the SiC raw material powder 5 sublimates to become a raw material gas 5a containing gaseous species Si, SiC 2 , Si 2 C, etc., and is transported to the upper SiC single crystal substrate 3,
Recrystallization is performed on the surface of the SiC single crystal substrate 3 at a relatively low temperature. At the same time, the arsenic or arsenic compound 6 previously added to the SiC raw material powder 5 sublimates or evaporates to become a gas 6a containing arsenic or arsenic compound. The gas 6a containing arsenic or an arsenic compound is mixed with the source gas 5a and then mixed with the source gas 5a.
And is taken into the growing SiC single crystal 4a as an n-type dopant.
【００３４】このようにして成長するＳｉＣ単結晶４ａ
は、珪素と原子半径が同等な砒素を導入するため、結晶
内に歪を発生させない。その結果、不純物の導入によ
り、例えば、６Ｈ型ＳｉＣの成長時に結晶内歪、すなわ
ち結晶面間隔が小さくなることで発生する１５Ｒ型Ｓｉ
Ｃのような異種多形を抑制することができる。よって、
所望の低抵抗率を有し、欠陥の少ない高品質なＳｉＣ単
結晶を成長させることができる。The SiC single crystal 4a thus grown
Introduces arsenic having an atomic radius equal to that of silicon, so that no distortion occurs in the crystal. As a result, for example, 15R-type Si generated by the introduction of impurities due to a reduction in intra-crystal distortion, that is, a decrease in crystal plane spacing during the growth of 6H-type SiC.
Heteropolymorphs such as C can be suppressed. Therefore,
It is possible to grow a high-quality SiC single crystal having a desired low resistivity and few defects.
【００３５】図２に、本発明の第２実施形態で用いる結
晶製造装置１０を示す。装置の基本構成および製造方法
は第１実施形態とほぼ同様であるため、以下、相違点を
中心に説明する。本実施形態の結晶製造装置１０は、黒
鉛容器１内にＳｉＣ原料粉末５を収容せず、底面に設け
たガス導入路１１からＳｉＣ原料ガス５ａを供給する。
原料ガス５ａとしては、ＳｉＣ昇華ガスの他、例えば、
シラン（ＳｉＨ4 ）とプロパン（Ｃ3 Ｈ8 ）の混合ガス
等を用いることができる。この原料ガス５ａとともに、
砒素または砒素化合物を含むガス６ａを、第１実施形態
と同様の温度勾配を設けた黒鉛容器１内に導入する。砒
素または砒素化合物を含むガス６ａとしては、例えば、
アルシン（ＡｓＨ3 ）等が好適に用いられる。FIG. 2 shows a crystal manufacturing apparatus 10 used in the second embodiment of the present invention. Since the basic configuration and manufacturing method of the device are almost the same as those of the first embodiment, the following description will focus on the differences. The crystal production apparatus 10 of the present embodiment does not store the SiC raw material powder 5 in the graphite container 1 and supplies the SiC raw material gas 5a from the gas introduction path 11 provided on the bottom surface.
As the source gas 5a, in addition to the SiC sublimation gas, for example,
A mixed gas of silane (SiH 4 ) and propane (C 3 H 8 ) can be used. Along with this raw material gas 5a,
The gas 6a containing arsenic or an arsenic compound is introduced into the graphite container 1 provided with the same temperature gradient as in the first embodiment. As the gas 6a containing arsenic or an arsenic compound, for example,
Arsine (AsH 3 ) or the like is preferably used.
【００３６】本実施形態では、砒素または砒素化合物を
含むガス６ａを用いるので、ＳｉＣ原料ガス５ａへの添
加、混合が容易である。そして、均一混合された原料ガ
スがＳｉＣ単結晶基板３に到達するので、砒素が単結晶
に均一に取り込まれ、局所的な結晶歪の発生を抑制する
効果が大きい。よって、所望の低抵抗率を有し、欠陥の
少ない高品質なＳｉＣ単結晶を成長させることができ
る。In this embodiment, since the gas 6a containing arsenic or an arsenic compound is used, addition and mixing to the SiC raw material gas 5a are easy. Then, since the uniformly mixed source gas reaches the SiC single crystal substrate 3, arsenic is uniformly taken into the single crystal, and the effect of suppressing the occurrence of local crystal distortion is great. Therefore, a high-quality SiC single crystal having a desired low resistivity and few defects can be grown.
【００３７】なお、ＳｉＣ原料ガスの供給源となるＳｉ
Ｃ原料粉末５を黒鉛容器１内に収容し、砒素または砒素
化合物を含むガス６ａのみをガス導入路から導入する構
成としてもよい。また、黒鉛容器１の構成材料中に砒素
または砒素化合物を添加して、ＳｉＣ原料粉末５を収容
し、ＳｉＣ原料粉末５を加熱昇華させた原料ガス５ａが
黒鉛容器１内表面に接触して反応する際に、原料ガス５
ａに砒素が取り込まれるようにしてもよい。あるいは、
黒鉛容器１内表面に、ＳｉＣよりなるコーティング層を
形成する場合に、このコーティング層に砒素または砒素
化合物を添加することもできる。いずれの場合も均一な
混合ガスを得るためには、黒鉛容器１またはコーティン
グ層に砒素を均一に含有させることが望ましい。The SiC source gas supply source Si
The C raw material powder 5 may be housed in the graphite container 1, and only the gas 6a containing arsenic or an arsenic compound may be introduced from the gas introduction path. Further, arsenic or an arsenic compound is added to the constituent material of the graphite container 1 to accommodate the SiC raw material powder 5, and the raw material gas 5a obtained by heating and sublimating the SiC raw material powder 5 contacts the inner surface of the graphite container 1 and reacts. When the raw material gas 5
Ar may be incorporated into a. Or,
When a coating layer made of SiC is formed on the inner surface of the graphite container 1, arsenic or an arsenic compound can be added to this coating layer. In any case, in order to obtain a uniform mixed gas, it is desirable that the graphite container 1 or the coating layer contains arsenic uniformly.
【００３８】図３に、本発明の第３実施形態で用いる結
晶製造装置１０を示す。装置の基本構成は第１実施形態
とほぼ同様であるため、以下、相違点を中心に説明す
る。本実施形態の方法では、砒素または砒素化合物に代
えて、珪素より小さな原子半径を有するｎ型ドーパント
原子、またはその化合物と、珪素より大きな原子半径を
有する軽金属を除く金属原子、またはその化合物を、Ｓ
ｉＣ単結晶に導入する。FIG. 3 shows a crystal manufacturing apparatus 10 used in the third embodiment of the present invention. Since the basic configuration of the apparatus is almost the same as that of the first embodiment, the following description will focus on the differences. In the method of the present embodiment, instead of arsenic or an arsenic compound, an n-type dopant atom having an atomic radius smaller than silicon, or a compound thereof, and a metal atom excluding a light metal having an atomic radius larger than silicon, or a compound thereof, S
It is introduced into an iC single crystal.
【００３９】本実施形態の結晶製造装置１０は、黒鉛容
器１内にＳｉＣ原料粉末５を収容するとともに、このＳ
ｉＣ原料粉末５に、珪素より大きな原子半径を有する金
属原子（軽金属を除く）またはその化合物を添加する。
軽金属（ナトリウム、カリウム、カルシウム、スカンジ
ウム等の密度が４ｇ／ｃｍ3 未満の金属）は珪素との原
子半径の差が大きく結晶欠陥の原因となり得るので、こ
れより原子半径の小さい金属原子、具体的には、原子半
径が１．１７オングストローム以上１．６０オングスト
ローム以下の金属または金属化合物７を添加するとよ
い。The crystal manufacturing apparatus 10 of this embodiment accommodates the SiC raw material powder 5 in the graphite container 1 and
A metal atom (excluding light metal) having an atomic radius larger than silicon or a compound thereof is added to the iC raw material powder 5.
Light metals (metals having a density of less than 4 g / cm 3 , such as sodium, potassium, calcium, and scandium) have a large difference in atomic radius from silicon and can cause crystal defects. , A metal or metal compound 7 having an atomic radius of 1.17 Å to 1.60 Å is preferably added.
【００４０】このような金属または金属化合物７として
は、例えば、チタン（原子半径１．４６オングストロー
ム）、バナジウム（原子半径１．３５オングストロー
ム）、タンタル（原子半径１．４７オングストローム）
が、金属化合物としては、これら金属の窒化物、炭化物
等が挙げられる。チタン、バナジウムは黒鉛容器１やＳ
ｉＣ原料粉末５に微量に含まれ得るので、添加が容易で
ある。また、タンタルはタンタル単体や炭化タンタルと
して容易に添加することができる。Examples of such a metal or metal compound 7 include titanium (atomic radius 1.46 angstroms), vanadium (atomic radius 1.35 angstroms), and tantalum (atomic radius 1.47 angstroms).
However, examples of the metal compound include nitrides and carbides of these metals. Titanium and vanadium are graphite containers 1 and S
Since it can be contained in a trace amount in the iC raw material powder 5, the addition is easy. Further, tantalum can be easily added as tantalum alone or tantalum carbide.
【００４１】そして、これらのうち少なくとも１種をＳ
ｉＣ原料粉末５に、予め混合し、上述したのと同様の方
法で、黒鉛容器１内に不活性ガスを導入し、ＳｉＣ原料
粉末５が２０００〜２５００℃となるように加熱する
と、ＳｉＣ原料粉末５の原料ガス５ａに、上記した金属
または金属化合物を含むガス７ａが混入する。And, at least one of them is S
When the SiC raw material powder 5 is preliminarily mixed with the iC raw material powder 5 and an inert gas is introduced into the graphite container 1 in the same manner as described above, and the SiC raw material powder 5 is heated to 2000 to 2500 ° C., The gas 7a containing the metal or metal compound described above is mixed with the source gas 5a of No. 5.
【００４２】一方、黒鉛台座２の外周には、ガス導入路
１２が設けられて、珪素より小さな原子半径を有するｎ
型ドーパント原子またはその化合物を含むガス、具体的
には、窒素（原子半径０．７０オングストローム）また
はリン（原子半径１．１０オングストローム）を含むガ
ス８ａが導入される。窒素またはリンを含むガス８ａ
は、黒鉛容器１内を加熱、減圧した時点で不活性ガスに
混合させて黒鉛容器１内に導入される。On the other hand, a gas introduction path 12 is provided on the outer periphery of the graphite pedestal 2 and has a smaller atomic radius than silicon.
A gas containing a type dopant atom or a compound thereof, specifically, a gas 8a containing nitrogen (atomic radius 0.70 angstroms) or phosphorus (atomic radius 1.10 angstroms) is introduced. Gas 8a containing nitrogen or phosphorus
Is mixed with an inert gas when the inside of the graphite container 1 is heated and decompressed, and is introduced into the graphite container 1.
【００４３】黒鉛容器１内の圧力を減圧して、０．１〜
１００Ｔｏｒｒ（１３．３Ｐａ〜１３．３ｋＰａ）に達
すると、昇華法成長が開始される。昇華法成長の際、黒
鉛容器１内のＳｉＣ単結晶基板３には、ＳｉＣの昇華ガ
スよりなる原料ガス５ａに、窒素またはリンを含むガス
８ａと金属または金属化合物を含むガス７ａとが混合さ
れた原料ガスが輸送され、それぞれｎ型ドーパントと金
属不純物としてＳｉＣ単結晶４ａに取り込まれる。The pressure in the graphite container 1 is reduced to 0.1 to
When the pressure reaches 100 Torr (13.3 Pa to 13.3 kPa), sublimation growth is started. During the sublimation growth, the SiC single crystal substrate 3 in the graphite container 1 is mixed with a gas 8a containing nitrogen or phosphorus and a gas 7a containing metal or a metal compound with a source gas 5a made of a sublimation gas of SiC. The source gas thus transported is taken into the SiC single crystal 4a as an n-type dopant and a metal impurity, respectively.
【００４４】ｎ型ドーパントとしての窒素またはリン
は、上記各実施形態における砒素と同様、ＳｉＣ単結晶
４ａの抵抗値を低減させる。ただし、ＳｉＣのＣサイト
に入る窒素は、炭素（原子半径０．７７オングストロー
ム）より原子半径が小さく、Ｓｉサイトに入るリンは、
珪素（原子半径１．１７オングストローム）より原子半
径が小さいため、結晶を圧縮させ結晶歪をもたらす方向
に作用する。これに対し、本実施形態で添加する不純物
としての金属原子は、珪素より原子半径が大きいため、
結晶を拡大させる作用を有する。すなわち、窒素または
リンを含むガス８ａと金属または金属化合物を含むガス
７ａの両方を、原料ガス５ａに混合することで、ｎ型ド
ーパントの圧縮作用を打ち消し、結晶内の歪を緩和する
効果が得られる。Nitrogen or phosphorus as the n-type dopant reduces the resistance value of the SiC single crystal 4a, similarly to arsenic in the above embodiments. However, nitrogen entering the C site of SiC has a smaller atomic radius than carbon (atomic radius 0.77 Å), and phosphorus entering the Si site is:
Since the atomic radius is smaller than that of silicon (atomic radius: 1.17 angstroms), it acts in the direction of compressing the crystal and causing crystal distortion. On the other hand, the metal atoms as impurities added in the present embodiment have a larger atomic radius than silicon,
It has the effect of expanding the crystal. That is, by mixing both the gas 8a containing nitrogen or phosphorus and the gas 7a containing a metal or a metal compound into the source gas 5a, the effect of negating the compressive action of the n-type dopant and relaxing strain in the crystal is obtained. Can be
【００４５】この時、ＳｉＣ単結晶４ａ中の窒素または
リン濃度は、１×１０16ｃｍ-3以上、１×１０20ｃｍ-3
以下とすることが好ましく、この範囲で、所望の低抵抗
値と良好な結晶性を両立することができる。砒素濃度が
１×１０16ｃｍ-3未満であると、抵抗値の低減効果が得
られず、１×１０20ｃｍ-3を越えるとＳｉＣ特性への悪
影響が懸念される。一方、ｎ型ドーパントによって生じ
る結晶歪の緩和効果を得るために、ＳｉＣ単結晶４ａ内
の金属不純物（例えば、チタン、バナジウム、タンタ
ル）濃度は、１×１０14ｃｍ-3以上とすることが必要で
ある。また、金属不純物濃度が大きくなると、ｎ型ドー
パントの添加による抵抗値の低減効果が打ち消されるの
で、これを避けるには、１×１０18ｃｍ-3、好適には、
１×１０16ｃｍ-3以下とすることが好ましい。通常、ｎ
型ドーパント濃度より約１〜２桁以上小さくなるように
濃度設定するとが望ましく、わずかな添加量で高い効果
が得られる。At this time, the concentration of nitrogen or phosphorus in the SiC single crystal 4a is 1 × 10 16 cm −3 or more and 1 × 10 20 cm −3.
The content is preferably set to the following range. Within this range, both a desired low resistance value and good crystallinity can be achieved. If the arsenic concentration is less than 1 × 10 16 cm −3 , the effect of reducing the resistance cannot be obtained. If the arsenic concentration exceeds 1 × 10 20 cm −3 , there is a concern that SiC characteristics may be adversely affected. On the other hand, in order to obtain the effect of alleviating the crystal strain caused by the n-type dopant, the concentration of metal impurities (for example, titanium, vanadium, tantalum) in the SiC single crystal 4a needs to be 1 × 10 14 cm −3 or more. It is. Further, when the metal impurity concentration is increased, the effect of reducing the resistance value due to the addition of the n-type dopant is negated. To avoid this, 1 × 10 18 cm −3 , preferably
It is preferable that the concentration be 1 × 10 16 cm −3 or less. Usually n
It is desirable to set the concentration so as to be lower than the mold dopant concentration by about one to two digits or more, and a high effect can be obtained with a small addition amount.
【００４６】その結果、結晶歪の小さいＳｉＣ単結晶４
ａが得られ、例えば、６Ｈ型ＳｉＣの成長時に結晶内
歪、すなわち結晶面間隔が小さくなることで発生する１
５Ｒ型ＳｉＣのような異種多形を抑制することができ
る。よって、所望の低抵抗率を有し、欠陥の少ない高品
質なＳｉＣ単結晶を成長させる上記各実施形態と同様の
効果が得られる。As a result, the SiC single crystal 4 having a small crystal strain
a is obtained, for example, due to intra-crystal distortion during growth of 6H-type SiC, that is, 1 caused by a decrease in the crystal plane spacing.
Heteropolymorphs such as 5R-type SiC can be suppressed. Therefore, the same effects as those of the above-described embodiments for growing a high-quality SiC single crystal having a desired low resistivity and few defects can be obtained.
【００４７】図４に、本発明の第４実施形態で用いる結
晶製造装置１０を示す。装置の基本構成および製造方法
は第３実施形態とほぼ同様であるため、以下、相違点を
中心に説明する。本実施形態の結晶製造装置１０は、ｎ
型ドーパントとなる窒素またはリンを含むガス８ａを外
部から導入する代わりに、黒鉛容器１内に収容したＳｉ
Ｃ原料粉末５に、原子半径が１．１７オングストローム
以上１．６０オングストローム以下の金属または金属化
合物７とともに、窒素化合物またはリン化合物８を添加
混合する。FIG. 4 shows a crystal manufacturing apparatus 10 used in the fourth embodiment of the present invention. Since the basic configuration and manufacturing method of the device are substantially the same as those of the third embodiment, the following description will focus on the differences. The crystal manufacturing apparatus 10 of the present embodiment has n
Instead of introducing a gas 8a containing nitrogen or phosphorus as a mold dopant from outside, Si contained in the graphite container 1 is used.
To the C raw material powder 5, a nitrogen compound or a phosphorus compound 8 is added and mixed together with a metal or a metal compound 7 having an atomic radius of 1.17 angstroms or more and 1.60 angstroms or less.
【００４８】これにより、ＳｉＣ原料粉末５の加熱昇華
時に、原料ガス５ａに、金属または金属化合物を含むガ
ス７ａと、窒素またはリンを含むガス８ａが混入され、
この混合ガスがＳｉＣ単結晶基板３に輸送される。よっ
て、第３実施形態と同様、ｎ型ドーパントとなる窒素ま
たはリンの圧縮作用を金属不純物が緩和することによっ
て、結晶歪の小さいＳｉＣ単結晶４ａが得られ、所望の
低抵抗率を有し、欠陥の少ない高品質なＳｉＣ単結晶を
成長させる同様の効果が得られる。As a result, during heating and sublimation of the SiC raw material powder 5, a gas 7a containing a metal or a metal compound and a gas 8a containing nitrogen or phosphorus are mixed into the raw material gas 5a,
This mixed gas is transported to SiC single crystal substrate 3. Therefore, as in the third embodiment, the metal impurity relaxes the compressive action of nitrogen or phosphorus as an n-type dopant, so that a SiC single crystal 4a with small crystal distortion is obtained, and a desired low resistivity is obtained. A similar effect of growing a high-quality SiC single crystal with few defects can be obtained.
【００４９】図５に、本発明の第５実施形態で用いる結
晶製造装置１０を示す。装置の基本構成および製造方法
は第３実施形態とほぼ同様であるため、以下、相違点を
中心に説明する。本実施形態の結晶製造装置１０は、原
子半径が１．１７オングストローム以上１．６０オング
ストローム以下の金属または金属化合物７を、黒鉛容器
１内に収容したＳｉＣ原料粉末５に添加せず、筒状体と
してＳｉＣ単結晶基板３下方の黒鉛容器１内表面に固定
する。ｎ型ドーパントとなる窒素またはリンを含むガス
８ａはガス導入路１２を経て外部から導入する。FIG. 5 shows a crystal manufacturing apparatus 10 used in the fifth embodiment of the present invention. Since the basic configuration and manufacturing method of the device are substantially the same as those of the third embodiment, the following description will focus on the differences. The crystal manufacturing apparatus 10 of the present embodiment does not add a metal or a metal compound 7 having an atomic radius of 1.17 angstroms or more and 1.60 angstroms or less to the SiC raw material powder 5 accommodated in the graphite container 1, Is fixed to the inner surface of the graphite container 1 below the SiC single crystal substrate 3. A gas 8a containing nitrogen or phosphorus serving as an n-type dopant is introduced from outside through a gas introduction path 12.
【００５０】このようにしても、ＳｉＣ原料粉末５の加
熱昇華時に、原料ガス５ａに、金属または金属化合物を
含むガス７ａと、窒素またはリンを含むガス８ａが混入
され、この混合ガスがＳｉＣ単結晶基板３に輸送され
る。よって、第３実施形態と同様、ｎ型ドーパントとな
る窒素またはリンの圧縮作用を金属不純物が緩和するこ
とによって、結晶歪の小さいＳｉＣ単結晶４ａが得ら
れ、所望の低抵抗率を有し、欠陥の少ない高品質なＳｉ
Ｃ単結晶を成長させる同様の効果が得られる。Also in this case, at the time of heating and sublimation of the SiC raw material powder 5, a gas 7a containing a metal or a metal compound and a gas 8a containing nitrogen or phosphorus are mixed into the raw material gas 5a, and this mixed gas It is transported to the crystal substrate 3. Therefore, as in the third embodiment, the metal impurity relaxes the compressive action of nitrogen or phosphorus as an n-type dopant, so that a SiC single crystal 4a with small crystal distortion is obtained, and a desired low resistivity is obtained. High quality Si with few defects
A similar effect of growing a C single crystal can be obtained.
【００５１】図６に、本発明の第６実施形態で用いる結
晶製造装置１０を示す。装置の基本構成および製造方法
は第３実施形態とほぼ同様であるため、以下、相違点を
中心に説明する。本実施形態の結晶製造装置１０は、Ｓ
ｉＣ原料粉末５を黒鉛容器１内に収容した添加せず、黒
鉛容器１底面に設けたガス導入路１１から、原料ガス５
ａを供給し、この原料ガス５ａとともに、原子半径が
１．１７オングストローム以上１．６０オングストロー
ム以下の金属または金属化合物を含むガス７ａと窒素ま
たはリンを含むガス８ａを導入する。FIG. 6 shows a crystal manufacturing apparatus 10 used in the sixth embodiment of the present invention. Since the basic configuration and manufacturing method of the device are substantially the same as those of the third embodiment, the following description will focus on the differences. The crystal manufacturing apparatus 10 of the present embodiment
The iC raw material powder 5 was stored in the graphite container 1 and was not added.
a, and together with the source gas 5a, a gas 7a containing a metal or a metal compound having an atomic radius of 1.17 to 1.60 angstroms or less and a gas 8a containing nitrogen or phosphorus are introduced.
【００５２】このようにすると、原料ガス５ａに、金属
または金属化合物を含むガス７ａと、窒素またはリンを
含むガス８ａを容易に混合でき、均一混合されたガスを
ＳｉＣ単結晶基板３に輸送できる。よって、第３実施形
態と同様、ｎ型ドーパントとなる窒素またはリンの圧縮
作用を金属不純物が緩和することによって、結晶歪の小
さいＳｉＣ単結晶４ａが得られ、所望の低抵抗率を有
し、欠陥の少ない高品質なＳｉＣ単結晶を成長させる同
様の効果が得られる。In this manner, the gas 7a containing a metal or a metal compound and the gas 8a containing nitrogen or phosphorus can be easily mixed into the raw material gas 5a, and the uniformly mixed gas can be transported to the SiC single crystal substrate 3. . Therefore, as in the third embodiment, the metal impurity relaxes the compressive action of nitrogen or phosphorus as an n-type dopant, so that a SiC single crystal 4a with small crystal distortion is obtained, and a desired low resistivity is obtained. A similar effect of growing a high-quality SiC single crystal with few defects can be obtained.
【００５３】[0053]
【実施例】（実施例１）上記図１に示した結晶製造装置
１０を用い、上記した方法でＳｉＣ単結晶の成長実験を
行った。黒鉛容器１に充填したＳｉＣ原料粉末５に、純
度９９％以上の金属砒素を、ＳｉＣに対する原子比が約
１０ｐｐｍ重量となるように混入した。ＳｉＣ単結晶基
板３は６Ｈ型を用い、Ｓｉ面を成長面とした。不活性ガ
ス雰囲気下、５００Ｔｏｒｒ（６６．６ｋＰａ）で、Ｓ
ｉＣ原料粉末５の温度が２３００℃、ＳｉＣ単結晶基板
３の温度が２２００℃となるように加熱した。その後、
減圧して約１００Ｔｏｒｒ（１３．３ｋＰａ）になった
時点で、約２０時間の単結晶成長を行った。その結果、
成長量８ｍｍの６Ｈ型のＳｉＣ単結晶４ａが得られた。EXAMPLES (Example 1) Using the crystal manufacturing apparatus 10 shown in FIG. 1 described above, an experiment for growing a SiC single crystal was performed by the method described above. Metal arsenic having a purity of 99% or more was mixed into the SiC raw material powder 5 filled in the graphite container 1 so that the atomic ratio to SiC was about 10 ppm by weight. The SiC single crystal substrate 3 was of 6H type, and the Si surface was used as a growth surface. Under an inert gas atmosphere at 500 Torr (66.6 kPa), S
The heating was performed so that the temperature of the iC raw material powder 5 was 2300 ° C. and the temperature of the SiC single crystal substrate 3 was 2200 ° C. afterwards,
When the pressure was reduced to about 100 Torr (13.3 kPa), a single crystal was grown for about 20 hours. as a result,
A 6H-type SiC single crystal 4a with a growth amount of 8 mm was obtained.
【００５４】得られたＳｉＣ単結晶４ａを断面スライス
し、ＴＥＭ（透過型電子顕微鏡）により電子線回折像か
ら面間隔を求めた。その結果、＜０００１＞方向の面間
隔は２．５２オングストロームで、文献値（ＰＲＯＰＥ
ＲＴＩＥＳ ＯＦ ＳＩＬＩＣＯＮ ＣＡＲＢＩＤＥ，
ｅｄｉｔｅｄ ｂｙ Ｇｅｒｙ Ｌ Ｈａｒｒｉｓ，ｅ
ｉｍｓ ＤＡＴＡＲＥＶＩＥＷ Ｓｅｒｉｅｓ Ｎｏ．
１３，ｐｐ．４．）と同等であった。また、結晶内歪と
して、ＳｉＣのＳｉまたはＣサイトに不純物（ここでは
砒素）が置換されたことによる結晶１ｍｏｌの体積変化
率を測定したところ、結晶内歪は０．５％以下であり、
歪のない高品質の結晶が得られた。ＳｉＣ単結晶４ａは
ｎ型で、砒素濃度は２．５×１０18ｃｍ-3、抵抗率は１
２０ｍΩｃｍであった。The obtained SiC single crystal 4a was sliced in cross section, and the plane spacing was determined from an electron diffraction image using a TEM (transmission electron microscope). As a result, the surface spacing in the <0001> direction was 2.52 angstroms, and the literature value (PROPE
RTIES OF SILICON CARBIDE,
edited by Gerry L Harris, e
ims DATAREVIEW Series No.
13, pp. 4. ). Further, when the volume change rate of 1 mol of the crystal due to the substitution of an impurity (here, arsenic) at the Si or C site of SiC was measured as the intra-crystal distortion, the intra-crystal distortion was 0.5% or less.
High quality crystals without distortion were obtained. The SiC single crystal 4a is n-type, the arsenic concentration is 2.5 × 10 18 cm −3 , and the resistivity is 1
It was 20 mΩcm.
【００５５】（実施例２）上記図２に示した結晶製造装
置１０を用い、上記した方法でＳｉＣ単結晶の成長実験
を行った。黒鉛容器１に、原料ガス５ａとしてシラン
（ＳｉＨ4 ）とプロパン（Ｃ3 Ｈ8 ）を３：１の容量比
で導入し、砒素または砒素化合物を含むガス８ａとして
アルシン（ＡｓＨ3 ）を、原料ガス５ａに対して約５ｐ
ｐｍ容量で混入した。黒鉛容器１ｂの内部圧力が約２０
０Ｔｏｒｒ（２６．６ｋＰａ）となるようにガス量を調
整した。ＳｉＣ単結晶基板３は６Ｈ型を用い、Ｓｉ面を
成長面とした。不活性ガス雰囲気下、５００Ｔｏｒｒ
（６６．６ｋＰａ）で、ＳｉＣ原料粉末５の温度が２３
００℃、ＳｉＣ単結晶基板３の温度が２２００℃となる
ように加熱した。その後、減圧して約１００Ｔｏｒｒ
（１３．３ｋＰａ）になった時点で、約２０時間の単結
晶成長を行った。その結果、成長量８ｍｍの６Ｈ型のＳ
ｉＣ単結晶４ａが得られた。Example 2 Using the crystal manufacturing apparatus 10 shown in FIG. 2, an experiment for growing a SiC single crystal was performed by the method described above. Silane (SiH 4 ) and propane (C 3 H 8 ) are introduced into the graphite container 1 at a volume ratio of 3: 1 as a source gas 5a, and arsine (AsH 3 ) is fed as a gas 8a containing arsenic or an arsenic compound. About 5p for gas 5a
Mixed in pm volume. The internal pressure of the graphite container 1b is about 20
The gas amount was adjusted to be 0 Torr (26.6 kPa). The SiC single crystal substrate 3 was of 6H type, and the Si surface was used as a growth surface. 500 Torr under inert gas atmosphere
(66.6 kPa) and the temperature of the SiC raw material powder 5 is 23
Heating was performed so that the temperature of the SiC single crystal substrate 3 was 2200 ° C. at 00 ° C. Then, reduce the pressure to about 100 Torr
(13.3 kPa), a single crystal was grown for about 20 hours. As a result, 6H type S with a growth amount of 8 mm
An iC single crystal 4a was obtained.
【００５６】得られたＳｉＣ単結晶４ａを断面スライス
し、ＴＥＭ（透過型電子顕微鏡）により電子線回折像か
ら面間隔を求めた。その結果、＜０００１＞方向の面間
隔は２．５２オングストロームで、文献値と同等であっ
た。また、結晶内歪は１％以下であり、歪のない高品質
の結晶が得られた。ＳｉＣ単結晶４ａはｎ型で、砒素濃
度は３．０×１０18ｃｍ-3、抵抗率は１００ｍΩｃｍで
あった。The obtained SiC single crystal 4a was sliced in cross section, and the plane spacing was determined from an electron diffraction image using a TEM (transmission electron microscope). As a result, the surface spacing in the <0001> direction was 2.52 Å, which was equivalent to the literature value. The strain in the crystal was 1% or less, and a high-quality crystal without distortion was obtained. The SiC single crystal 4a was n-type, had an arsenic concentration of 3.0 × 10 18 cm −3 , and a resistivity of 100 mΩcm.
【００５７】（実施例３）上記図３に示した結晶製造装
置１０を用い、上記した方法でＳｉＣ単結晶の成長実験
を行った。黒鉛容器１に充填したＳｉＣ原料粉末５に、
金属または金属化合物７として、純度９９％以上の金属
チタン（Ｔｉ）を、ＳｉＣに対する原子比が約５ｐｐｍ
重量となるように混入した。ＳｉＣ単結晶基板３は６Ｈ
型を用い、Ｓｉ面を成長面とした。不活性ガス雰囲気
下、５００Ｔｏｒｒ（６６．６ｋＰａ）で、ＳｉＣ原料
粉末５の温度が２３００℃、ＳｉＣ単結晶基板３の温度
が２２００℃となるように加熱した。その後、減圧して
約１００Ｔｏｒｒ（１３．３ｋＰａ）になった時点で、
窒素またはリンを含むガス８ａとして、窒素を不活性ガ
スに対して約０．１％容量混入した。その後、約２０時
間の単結晶成長を行った結果、成長量８ｍｍの６Ｈ型の
ＳｉＣ単結晶４ａが得られた。Example 3 Using the crystal manufacturing apparatus 10 shown in FIG. 3, an experiment for growing a SiC single crystal was performed by the method described above. The SiC raw material powder 5 filled in the graphite container 1
As the metal or metal compound 7, metal titanium (Ti) having a purity of 99% or more and an atomic ratio to SiC of about 5 ppm
It was mixed so as to be weight. The SiC single crystal substrate 3 is 6H
Using a mold, the Si surface was used as the growth surface. Heating was performed under an inert gas atmosphere at 500 Torr (66.6 kPa) such that the temperature of the SiC raw material powder 5 became 2300 ° C. and the temperature of the SiC single crystal substrate 3 became 2200 ° C. Then, when the pressure was reduced to about 100 Torr (13.3 kPa),
As the gas 8a containing nitrogen or phosphorus, about 0.1% by volume of nitrogen was mixed with the inert gas. Thereafter, a single crystal was grown for about 20 hours, and as a result, a 6H-type SiC single crystal 4a with a growth amount of 8 mm was obtained.
【００５８】得られたＳｉＣ単結晶４ａを断面スライス
し、ＴＥＭ（透過型電子顕微鏡）により電子線回折像か
ら面間隔を求めた。その結果、＜０００１＞方向の面間
隔は２．５１オングストロームで、文献値と同等であっ
た。また、結晶内歪は１％以下であり、歪のない高品質
の結晶が得られた。ＳｉＣ単結晶４ａはｎ型で、窒素濃
度は６．０×１０18ｃｍ-3、チタン濃度は５．０×１０
15ｃｍ-3、抵抗率は６０ｍΩｃｍであった。The cross section of the obtained SiC single crystal 4a was sliced, and the plane spacing was determined from an electron diffraction image using a TEM (transmission electron microscope). As a result, the surface spacing in the <0001> direction was 2.51 Å, which was equivalent to the literature value. The strain in the crystal was 1% or less, and a high-quality crystal without distortion was obtained. SiC single crystal 4a is n-type, the nitrogen concentration of 6.0 × 10 18 cm -3, the concentration of titanium 5.0 × 10
The resistivity was 15 cm -3 and the resistivity was 60 mΩcm.
【００５９】なお、金属または金属化合物７として、金
属チタン（Ｔｉ）に代えて、窒化チタン（ＴｉＮ）、バ
ナジウム（Ｖ）、窒化バナジウム（ＶＮ）、炭化バナジ
ウム（ＶＣ）、タンタル（Ｔａ）、炭化タンタル（Ｔａ
Ｃ）、窒化タンタル（ＴａＮ）を約０．５〜５ｐｐｍ重
量となるように混入した場合、窒素またはリンを含むガ
ス８ａとして、窒素に代えてリン（Ｐ2 、Ｐ4 ）を約
０．０５〜０．１％容量混入した場合も、同様の結果が
得られた。As the metal or metal compound 7, titanium nitride (TiN), vanadium (V), vanadium nitride (VN), vanadium carbide (VC), tantalum (Ta), tantalum (Ta) are used in place of titanium metal (Ti). Tantalum (Ta
C), when tantalum nitride (TaN) is mixed so as to have a weight of about 0.5 to 5 ppm, as a gas 8a containing nitrogen or phosphorus, phosphorus (P 2 , P 4 ) is replaced by about 0.05 Similar results were obtained when the volume was mixed by 0.1%.
【００６０】（実施例４）上記図４に示した結晶製造装
置１０を用い、上記した方法でＳｉＣ単結晶の成長実験
を行った。黒鉛容器１に充填したＳｉＣ原料粉末５に、
窒素またはリンの化合物８として、純度９９％以上の金
属リン（Ｐ）を、ＳｉＣに対する原子比が約５０ｐｐｍ
重量となるように混入した。さらに、金属または金属化
合物７として、純度９９％以上の金属チタン（Ｔｉ）
を、ＳｉＣに対する原子比が約５ｐｐｍ重量となるよう
に混入した。ＳｉＣ単結晶基板３は６Ｈ型を用い、Ｓｉ
面を成長面とした。不活性ガス雰囲気下、５００Ｔｏｒ
ｒ（６６．６ｋＰａ）で、ＳｉＣ原料粉末５の温度が２
３００℃、ＳｉＣ単結晶基板３の温度が２２００℃とな
るように加熱した。その後、減圧して約１００Ｔｏｒｒ
（１３．３ｋＰａ）になった時点で、約２０時間の単結
晶成長を行った。その結果、成長量８ｍｍの６Ｈ型のＳ
ｉＣ単結晶４ａが得られた。Example 4 Using the crystal manufacturing apparatus 10 shown in FIG. 4, an experiment for growing a SiC single crystal was performed by the method described above. The SiC raw material powder 5 filled in the graphite container 1
As compound 8 of nitrogen or phosphorus, metal phosphorus (P) having a purity of 99% or more, and an atomic ratio to SiC of about 50 ppm
It was mixed so as to be weight. Further, as the metal or metal compound 7, metal titanium (Ti) having a purity of 99% or more
Was incorporated so that the atomic ratio to SiC was about 5 ppm by weight. The 6C type SiC single crystal substrate 3 is used,
The surface was defined as the growth surface. 500 Torr under inert gas atmosphere
r (66.6 kPa), the temperature of the SiC raw material powder 5 is 2
The heating was performed such that the temperature of the SiC single crystal substrate 3 was 300 ° C. and 2200 ° C. Then, reduce the pressure to about 100 Torr
(13.3 kPa), a single crystal was grown for about 20 hours. As a result, 6H-type S with a growth amount of 8 mm
An iC single crystal 4a was obtained.
【００６１】得られたＳｉＣ単結晶４ａを断面スライス
し、ＴＥＭ（透過型電子顕微鏡）により電子線回折像か
ら面間隔を求めた。その結果、＜０００１＞方向の面間
隔は２．５１オングストロームで、文献値と同等であっ
た。また、結晶内歪は１％以下であり、歪のない高品質
の結晶が得られた。ＳｉＣ単結晶４ａはｎ型で、リン濃
度は２．５×１０18ｃｍ-3、チタン濃度は５．０×１０
15ｃｍ-3、抵抗率は１２０ｍΩｃｍであった。The cross section of the obtained SiC single crystal 4a was sliced, and the plane spacing was determined from an electron diffraction image by a TEM (transmission electron microscope). As a result, the surface spacing in the <0001> direction was 2.51 Å, which was equivalent to the literature value. The strain in the crystal was 1% or less, and a high-quality crystal without distortion was obtained. The SiC single crystal 4a is n-type, the phosphorus concentration is 2.5 × 10 18 cm −3 , and the titanium concentration is 5.0 × 10
The resistivity was 15 cm -3 and the resistivity was 120 mΩcm.
【００６２】（比較例１）比較のため、上記図７に示し
た結晶製造装置１０を用い、上記した方法でＳｉＣ単結
晶の成長実験を行った。黒鉛容器１に充填されるＳｉＣ
原料粉末５には、純度９９％以上のＳｉＣを用いた。Ｓ
ｉＣ単結晶基板３は６Ｈ型を用い、Ｓｉ面を成長面とし
た。不活性ガス雰囲気下、５００Ｔｏｒｒ（６６．６ｋ
Ｐａ）で、ＳｉＣ原料粉末５の温度が２３００℃、Ｓｉ
Ｃ単結晶基板３の温度が２２００℃となるように加熱し
た。その後、減圧して約１００Ｔｏｒｒ（１３．３ｋＰ
ａ）になった時点で、窒素を含むガス８ｂとして、窒素
を不活性ガスに対して約０．１％容量混入した。その
後、約２０時間の単結晶成長を行った結果、成長量８ｍ
ｍの６Ｈ型と１５Ｒ型が混在したＳｉＣ単結晶４ｂが得
られた。(Comparative Example 1) For comparison, an experiment for growing a SiC single crystal was performed by the above-described method using the crystal manufacturing apparatus 10 shown in FIG. SiC filled in graphite container 1
As raw material powder 5, SiC having a purity of 99% or more was used. S
The iC single crystal substrate 3 was of a 6H type, and the Si surface was used as a growth surface. 500 Torr (66.6k) under an inert gas atmosphere
Pa), the temperature of the SiC raw material powder 5 is 2300 ° C.,
The C single crystal substrate 3 was heated so as to have a temperature of 2200 ° C. Then, the pressure was reduced to about 100 Torr (13.3 kP
At the time of a), about 0.1% by volume of nitrogen was mixed with the inert gas as the nitrogen-containing gas 8b. After that, a single crystal was grown for about 20 hours.
As a result, a SiC single crystal 4b having a mixture of 6H type and 15R type m was obtained.
【００６３】得られたＳｉＣ単結晶４ａを断面スライス
し、ＴＥＭ（透過型電子顕微鏡）により電子線回折像か
ら面間隔を求めた。その結果、＜０００１＞方向の面間
隔は文献値より小さい２．４８オングストロームであっ
た。また、結晶内歪は１．５％以上であり、歪が生じた
結果、１５Ｒ型が発生したことが分かった。ＳｉＣ単結
晶４ｂはｎ型で、窒素濃度は６．０×１０18ｃｍ-3、抵
抗率は６０ｍΩｃｍであった。The obtained SiC single crystal 4a was sliced in section, and the plane spacing was determined from an electron diffraction image by a TEM (transmission electron microscope). As a result, the surface spacing in the <0001> direction was 2.48 angstroms, which was smaller than the literature value. In addition, the strain in the crystal was 1.5% or more, and as a result of the strain, it was found that the 15R type was generated. SiC single crystal 4b was n-type, had a nitrogen concentration of 6.0 × 10 18 cm −3 , and a resistivity of 60 mΩcm.
【図１】本発明の第１実施形態における結晶製造装置の
構成を示す図である。FIG. 1 is a diagram showing a configuration of a crystal manufacturing apparatus according to a first embodiment of the present invention.
【図２】本発明の第２実施形態における結晶製造装置の
構成を示す図である。FIG. 2 is a diagram illustrating a configuration of a crystal manufacturing apparatus according to a second embodiment of the present invention.
【図３】本発明の第３実施形態における結晶製造装置の
構成を示す図である。FIG. 3 is a diagram illustrating a configuration of a crystal manufacturing apparatus according to a third embodiment of the present invention.
【図４】本発明の第４実施形態における結晶製造装置の
構成を示す図である。FIG. 4 is a diagram illustrating a configuration of a crystal manufacturing apparatus according to a fourth embodiment of the present invention.
【図５】本発明の第５実施形態における結晶製造装置の
構成を示す図である。FIG. 5 is a diagram illustrating a configuration of a crystal manufacturing apparatus according to a fifth embodiment of the present invention.
【図６】本発明の第６実施形態における結晶製造装置の
構成を示す図である。FIG. 6 is a diagram illustrating a configuration of a crystal manufacturing apparatus according to a sixth embodiment of the present invention.
【図７】従来の結晶製造装置の構成を示す図である。FIG. 7 is a diagram showing a configuration of a conventional crystal manufacturing apparatus.
１０ 結晶製造装置 １ａ、１ｂ 黒鉛容器 ２ 黒鉛台座 ３ 炭化珪素単結晶基板 ４ａ、４ｂ 炭化珪素単結晶 ５ 炭化珪素原料粉末 ５ａ 原料ガス ６ 砒素または砒素化合物 ６ａ 砒素または砒素化合物を含むガス ７ 金属または金属化合物 ７ａ 金属または金属化合物を含むガス ８ 窒素またはリンの化合物 ８ａ 窒素またはリンを含むガス DESCRIPTION OF SYMBOLS 10 Crystal manufacturing apparatus 1a, 1b Graphite container 2 Graphite pedestal 3 Silicon carbide single crystal substrate 4a, 4b Silicon carbide single crystal 5 Silicon carbide raw material powder 5a Raw material gas 6 Arsenic or arsenic compound 6a Gas containing arsenic or arsenic compound 7 Metal or metal Compound 7a Gas containing metal or metal compound 8 Compound of nitrogen or phosphorus 8a Gas containing nitrogen or phosphorus
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久野 裕也 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 (72)発明者 永久保 雅夫 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 (72)発明者 恩田 正一 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 Ｆターム(参考） 4G077 AA02 BE08 DA01 DA19 DB04 DB07 EB01 HA12 5F045 AA06 AB06 AC01 AC07 AC19 AD18 AE25 BB11 CA09 5F103 AA01 DD17 GG01 HH03 JJ03 KK10 LL02 RR06 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuya Kuno 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Denso Corporation (72) Inventor Masao Eibo 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Denso Corporation (72) Inventor Shoichi Onda 1-1-1, Showa-cho, Kariya-shi, Aichi F-term in DENSO Corporation (reference) 4G077 AA02 BE08 DA01 DA19 DB04 DB07 EB01 HA12 5F045 AA06 AB06 AC01 AC07 AC19 AD18 AE25 BB11 CA09 5F103 AA01 DD17 GG01 HH03 JJ03 KK10 LL02 RR06
Claims (18)
炭化珪素原料ガスを供給して炭化珪素単結晶を成長させ
る炭化珪素単結晶の製造方法において、上記炭化珪素原
料ガスに砒素または砒素化合物を添加することを特徴と
する炭化珪素単結晶の製造方法。1. A silicon carbide single crystal substrate serving as a seed crystal,
A method for producing a silicon carbide single crystal, wherein a silicon carbide raw material gas is supplied to grow a silicon carbide single crystal, wherein arsenic or an arsenic compound is added to the silicon carbide raw material gas.
上記炭化珪素原料ガスの供給源となる炭化珪素原料粉末
を配置し、該炭化珪素原料粉末に砒素または砒素化合物
を添加することにより、上記炭化珪素原料ガスに砒素ま
たは砒素化合物を添加する請求項１記載の炭化珪素単結
晶の製造方法。2. A silicon carbide single crystal substrate, wherein
2. An arsenic or arsenic compound is added to said silicon carbide raw material gas by arranging a silicon carbide raw material powder serving as a supply source of said silicon carbide raw material gas and adding arsenic or an arsenic compound to said silicon carbide raw material powder. The method for producing a silicon carbide single crystal according to the above.
置し、上記容器内に砒素または砒素化合物を含有する部
材を配置するか、あるいは、上記容器の少なくとも内表
面に砒素または砒素化合物を含有させることにより、上
記炭化珪素原料ガスに砒素または砒素化合物を添加する
請求項１記載の炭化珪素単結晶の製造方法。3. The method according to claim 1, wherein the silicon carbide single crystal substrate is disposed in a container, and a member containing arsenic or an arsenic compound is disposed in the container, or arsenic or an arsenic compound is disposed on at least an inner surface of the container. The method for producing a silicon carbide single crystal according to claim 1, wherein arsenic or an arsenic compound is added to the silicon carbide raw material gas by containing.
置し、上記容器内に砒素または砒素化合物を含有するガ
スを供給することにより、上記炭化珪素原料ガスに砒素
または砒素化合物を添加する請求項１記載の炭化珪素単
結晶の製造方法。4. Arsenic or an arsenic compound is added to the silicon carbide raw material gas by disposing the silicon carbide single crystal substrate in a container and supplying a gas containing arsenic or an arsenic compound into the container. The method for producing a silicon carbide single crystal according to claim 1.
炭化珪素原料ガスを供給して炭化珪素単結晶を成長させ
る炭化珪素単結晶の製造方法において、上記炭化珪素原
料ガスに、珪素より小さな原子半径を有するｎ型ドーパ
ント原子またはその化合物と、珪素より大きな原子半径
を有する軽金属を除く金属原子またはその化合物を添加
することを特徴とする炭化珪素単結晶の製造方法。5. A silicon carbide single crystal substrate serving as a seed crystal,
In the method for producing a silicon carbide single crystal in which a silicon carbide raw material gas is supplied to grow a silicon carbide single crystal, the silicon carbide raw material gas includes an n-type dopant atom having a smaller atomic radius than silicon or a compound thereof, A method for producing a silicon carbide single crystal, characterized by adding a metal atom other than a light metal having an atomic radius or a compound thereof.
パント原子の添加量より少なく、上記ｎ型ドーパント原
子により生じる結晶内歪を緩和するために必要な量以上
とする請求項５記載の炭化珪素単結晶の製造方法。6. The method according to claim 5, wherein the amount of addition of the metal atom is smaller than the amount of addition of the n-type dopant atom, and is equal to or more than an amount necessary to reduce intra-crystal distortion caused by the n-type dopant atom. A method for producing a silicon carbide single crystal.
リンから選ばれる少なくとも１つである請求項５または
６記載の炭化珪素単結晶の製造方法。7. The method for producing a silicon carbide single crystal according to claim 5, wherein said n-type dopant atom is at least one selected from nitrogen and phosphorus.
ングストローム以上、１．６０オングストローム以下の
原子である請求項５ないし７のいずれかに記載の炭化珪
素単結晶の製造方法。8. The method for producing a silicon carbide single crystal according to claim 5, wherein said metal atom is an atom having an atomic radius of 1.17 angstroms or more and 1.60 angstroms or less.
よびタンタルから選ばれる少なくとも１つである請求項
８記載の炭化珪素単結晶の製造方法。9. The method for producing a silicon carbide single crystal according to claim 8, wherein said metal atom is at least one selected from titanium, vanadium and tantalum.
配置し、上記容器内に上記ｎ型ドーパント原子またはそ
の化合物を含有するガスを供給することにより、上記炭
化珪素原料ガスに上記ｎ型ドーパント原子またはその化
合物を添加する請求項５ないし９のいずれかに記載の炭
化珪素単結晶の製造方法。10. The silicon carbide single crystal substrate is placed in a container, and a gas containing the n-type dopant atom or a compound thereof is supplied into the container, whereby the n-type silicon carbide raw material gas is added to the silicon carbide raw material gas. The method for producing a silicon carbide single crystal according to claim 5, wherein a dopant atom or a compound thereof is added.
と、上記原料炭化珪素ガスの供給源となる炭化珪素原料
粉末を配置し、該炭化珪素原料粉末に上記金属原子また
はその化合物を添加することにより、上記炭化珪素原料
ガスに上記金属原子またはその化合物を添加する請求項
５ないし１０のいずれかに記載の炭化珪素単結晶の製造
方法。11. A silicon carbide single crystal substrate and a silicon carbide raw material powder serving as a source of the raw material silicon carbide gas are arranged in a container, and the metal atom or a compound thereof is added to the silicon carbide raw material powder. 11. The method for producing a silicon carbide single crystal according to claim 5, wherein the metal atom or a compound thereof is added to the silicon carbide source gas.
配置し、上記容器内に、上記金属原子またはその化合物
を含有する部材を配置するか、あるいは、上記容器の少
なくとも内表面に上記金属原子またはその化合物を含有
させることにより、上記炭化珪素原料ガスに上記金属原
子またはその化合物を添加する請求項５ないし１０のい
ずれかに記載の炭化珪素単結晶の製造方法。12. The silicon carbide single crystal substrate is placed in a container, and a member containing the metal atom or its compound is placed in the container, or the metal is placed on at least the inner surface of the container. The method for producing a silicon carbide single crystal according to any one of claims 5 to 10, wherein the metal atom or the compound thereof is added to the silicon carbide source gas by containing an atom or a compound thereof.
配置し、上記容器内に上記金属原子またはその化合物を
含有するガスを供給することにより、上記炭化珪素原料
ガスに上記金属原子またはその化合物を添加する請求項
５ないし１０のいずれかに記載の炭化珪素単結晶の製造
方法。13. The silicon carbide single crystal substrate is placed in a container, and a gas containing the metal atom or a compound thereof is supplied into the container. The method for producing a silicon carbide single crystal according to claim 5, wherein a compound is added.
徴とする炭化珪素単結晶。14. A silicon carbide single crystal characterized by containing arsenic in the crystal structure.
×１０20ｃｍ-3以下である請求項１４記載の炭化珪素単
結晶。15. An arsenic concentration of 1 × 10 16 cm −3 or more,
× 10 20 cm -3 silicon carbide single crystal by a claim 14 or less.
径を有するｎ型ドーパント原子と、珪素より大きな原子
半径を有する軽金属を除く金属原子を含有することを特
徴とする炭化珪素単結晶。16. A silicon carbide single crystal comprising a crystal structure containing an n-type dopant atom having an atomic radius smaller than that of silicon and a metal atom excluding a light metal having an atomic radius larger than silicon.
０16ｃｍ-3以上、１×１０20ｃｍ-3以下である請求項１
６記載の炭化珪素単結晶。17. The method according to claim 17, wherein the n-type dopant atom concentration is 1 × 1.
2. The thickness is not less than 0 16 cm −3 and not more than 1 × 10 20 cm −3.
6. The silicon carbide single crystal according to 6.
以上、１×１０18ｃｍ-3以下である請求項１６または１
７記載の炭化珪素単結晶。18. The method according to claim 18, wherein the metal atom concentration is 1 × 10 14 cm −3.
17 or more, 1 × 10 18 cm −3 or less.
7. The silicon carbide single crystal according to 7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001030477A JP3876628B2 (en) | 2001-02-07 | 2001-02-07 | Method for producing silicon carbide single crystal and silicon carbide single crystal |
| US10/058,353 US20020104478A1 (en) | 2001-02-07 | 2002-01-30 | Silicon carbide single crystal and process for producing the same |
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| JP2001030477A JP3876628B2 (en) | 2001-02-07 | 2001-02-07 | Method for producing silicon carbide single crystal and silicon carbide single crystal |
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2002
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| US20020104478A1 (en) | 2002-08-08 |
| JP3876628B2 (en) | 2007-02-07 |
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